# US 5,348,838 A · Photosensitive composition comprising alkali soluble binder and photoacid generator having sulfonyl group > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,348,838 A - Document ID: US5348838A - Status: Granted - Kind: A - Application number: 07/921,692 - Filed: 1992-07-30 - Granted: 1994-09-20 - Earliest claimed: 1991-07-31 - Assignees: Kabushiki Kaisha Toshiba - Inventors: Toru Ushirogouchi; Naoko Kihara; Osamu Sasaki; Tsukasa Tada; Takuya Naito; Satoshi Saito - Web page: https://patentgrep.com/patent/US5348838A ## CPC - C08G 8/28: Chemically modified polycondensates - C08K 5/41: Compounds containing sulfur bound to oxygen - G03F 7/0045: {with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors} - Y10S 430/11: Vinyl alcohol polymer or derivative - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G) - Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS ## Abstract A photosensitive composition comprises an alkali-soluble resin, a compound which has a substituent group decomposable by an acid and generates an alkali-soluble group upon decomposition of the substituent group, or a compound which has a substituent group capable of crosslinking the alkali-soluble resin in the presence of an acid, and a compound which generates an acid upon exposure, which is represented by formula (1) given below: ##STR1## wherein R.sub.11 represents a monovalent organic group or a monovalent organic group into which at least one selected from the group consisting of a halogen atom, a nitro group, and a cyano group is introduced, each of R.sub.12, R.sub.13, and R.sub.14 independently represents hydrogen, a halogen atom, a nitro group, a cyano group, a monovalent organic group, or a monovalent organic group into which at least one selected from the group consisting of a halogen atom, a nitro group, and a cyano group is introduced. ## Claims ### Claim 1 A photosensitive composition comprising: an alkali-soluble resin; a compound which has a substituent group decomposable by an acid and generates an alkali-soluble group upon decomposition of the substituent group, or an aminoplast resin which has a substituent group capable of crosslinking the alkali-soluble resin in the presence of an acid; and a compound which generates an acid upon exposure, which is represented by formula (1) given below: ##STR95## wherein R.sub.11 represents a monovalent organic group, or a monovalent organic group into which at least one substituent selected from the group consisting of a halogen atom, a nitro group, and a cyano group is introduced, each of the R.sub.12, R.sub.13, and R.sub.14 independently represents hydrogen, a halogen atom, a nitro group, a cyano group, a monovalent organic group, or a monovalent organic group into which at least one substituent selected from the group consisting of a halogen atom, a nitro group, and a cyano group is introduced. ### Claim 2 (depends on 1) The composition according to claim 1, wherein at least one of R.sub.12, R.sub.13, and R.sub.14 in formula (1) is a cyano group. ### Claim 3 (depends on 1) The composition according to claim 1, wherein at least one of R.sub.12, R.sub.13, and R.sub.14 in formula (1) is hydrogen. ### Claim 4 (depends on 1) The composition according to claim 1, wherein R.sub.11 in formula (1) is an aromatic group. ### Claim 5 (depends on 1) The composition according to claim 1, wherein a content of the compound represented by formula (1) is at least about not less than 0.1 part by weight and less than about 40 parts by weight based on 100 parts by weight of a content of the alkali-soluble resin. ### Claim 6 (depends on 1) The composition according to claim 1, wherein the alkali-soluble resin is a phenolic novolak resin. ### Claim 7 (depends on 1) The composition according to claim 1, wherein the alkali-soluble resin has a softening point of not less than 150.degree. C. and an average molecular weight of about 3,000 to 8,000. ### Claim 8 (depends on 1) The composition according to claim 1, wherein the compound having the substituent group decomposable by the acid is converted into a compound which generates --COO-- or --SO.sub.3 -- by a behavior of an alkaline solution after decomposition of the substituent group by the acid. ### Claim 9 (depends on 8) The composition according to claim 8, wherein the compound having the substituent group decomposable by the acid is a compound represented by formula (4) given below: ##STR96## wherein R.sub.41 and R.sub.42 may be the same or different and each represents hydrogen, a halogen atom, a cyano group, a nitro group, a silyl group, or a monovalent organic group; R.sub.41 and R.sub.42 may be combined to form a ring; X represents >C.dbd.O or --SO.sub.2 --; Y represents a bivalent organic group; and at least one of R.sub.41, R.sub.42, and Y has the substituent group decomposable by the acid. ### Claim 10 (depends on 9) The composition according to claim 9, wherein a content of the compound represented by formula (4) falls within a range of about 3 to 40 parts by weight based on 100 parts by weight of a content of the alkali-soluble resin. ### Claim 11 A photosensitive composition comprising: an alkali-soluble resin; a compound which has a substituent group decomposable by an acid and generates an alkali-soluble group upon decomposition of the substituent group, or an aminoplast resin which has a substituent group capable of crosslinking the alkali-soluble resin in the presence of an acid; and a compound which generates an acid upon exposure, which is represented by formula (2) given below: ##STR97## wherein each of R.sub.21 and R.sub.23 independently represents a monovalent organic group, or a monovalent organic group into which at least one substituent selected from the group consisting of a halogen atom, a nitro group, and a cyano group is introduced, and R.sub.22 represents a sulfonyl or carbonyl group. ### Claim 12 (depends on 11) The composition according to claim 11, wherein at least one of R.sub.21 and R.sub.23 in formula (2) is an aromatic group. ### Claim 13 (depends on 11) The composition according to claim 11, wherein a content of the compound represented by formula (2) is at least about not less than 0.1 part by weight and less than about 40 parts by weight based on 100 parts by weight of a content of the alkali-soluble resin. ### Claim 14 (depends on 11) The composition according to claim 11, wherein the alkali-soluble resin is a phenolic novolak resin. ### Claim 15 (depends on 11) The composition according to claim 11, wherein the alkali-soluble resin has a softening point of not less than 150.degree. C. and an average molecular weight of about 3,000 to 8,000. ### Claim 16 (depends on 11) The composition according to claim 11, wherein the compound having the substituent group decomposable by the acid is converted into a compound which generates --COO-- or --SO.sub.3 -- by a behavior of an alkaline solution after decomposition of the substituent group by the acid. ### Claim 17 (depends on 16) The composition according to claim 16, wherein the compound having the substituent group decomposable by the acid is a compound represented by formula (4) given below: ##STR98## wherein R.sub.41 and R.sub.42 may be the same or different and each represents hydrogen, a halogen atom, a cyano group, a nitro group, a silyl group, or a monovalent organic group; R.sub.41 and R.sub.42 may be combined to form a ring; X represents >C.dbd.O or --SO.sub.2 --; Y represents a bivalent organic group; and at least one of R.sub.41, R.sub.42, and Y has the substituent group decomposable by the acid. ### Claim 18 (depends on 17) The composition according to claim 17, wherein a content of the compound represented by formula (4) falls within a range of about 3 to 40 parts by weight based on 100 parts by weight of a content of the alkali-soluble resin. ### Claim 19 A photosensitive composition comprising: an alkali-soluble resin; a compound which has a substituent group decomposable by an acid and generates an alkali-soluble group upon decomposition of the substituent group; and a compound which generates an acid upon exposure, which is represented by formula (3) given below: ##STR99## wherein each of R.sub.31, R.sub.32, and R.sub.35 independently represents a monovalent organic group, or a monovalent organic group into which at least one substituent selected from the group consisting of a halogen atom, a nitro group, and a cyano group is introduced, R.sub.33 represents hydrogen, a monovalent organic group, or a monovalent organic group into which at least one substituent selected from the group consisting of a halogen atom, a nitro group, and a cyano group is introduced, and R.sub.34 represents a sulfonyl group, a sulfinyl group, a sulfur atom, or a carbonyl group. ### Claim 20 (depends on 19) The composition according to claim 19, wherein R.sub.34 in formula (3) is a sulfonyl group. ### Claim 21 (depends on 19) The composition according to claim 19, wherein at least one of R.sub.31, R.sub.32, and R.sub.35 is an aromatic group. ### Claim 22 (depends on 19) The composition according to claim 19, wherein a content of the compound represented by formula (3) is at least about not less than 0.1 part by weight and less than about 40 parts by weight based on 100 parts by weight of a content of the alkali-soluble resin. ### Claim 23 (depends on 19) The composition according to claim 19, wherein the alkali-soluble resin is a phenolic novolak resin. ### Claim 24 (depends on 19) A composition according to claim 19, wherein the alkali-soluble resin has a softening point of not less than 150.degree. C. and an average molecular weight of about 3,000 to 8,000. ### Claim 25 (depends on 19) The composition according to claim 19, wherein the compound having the substituent group decomposable by the acid is converted into a compound which generates --COO-- or --SO.sub.3 -- by a behavior of an alkaline solution after decomposition of the substituent group by the acid. ### Claim 26 (depends on 25) The composition according to claim 25, wherein the compound having the substituent group decomposable by the acid is a compound represented by formula (4) given below: ##STR100## wherein R.sub.41 and R.sub.42 may be the same or different and each represents hydrogen, a halogen atom, a cyano group, a nitro group, a silyl group, or a monovalent organic group; R.sub.41 and R.sub.42 may be combined to form a ring; X represents >C.dbd.O or --SO.sub.2 --; Y represents a bivalent organic group; and at least one of R.sub.41, R.sub.42, and Y has the substituent group decomposable by the acid. ### Claim 27 (depends on 26) The composition according to claim 26, wherein a content of the compound represented by formula (4) falls within a range of about 3 to 40 parts by weight based on 100 parts by weight of a content of the alkali-soluble resin. ### Claim 28 A composition containing 0 to 30 parts by weight of poly-vinylphenol, 30 to 100 parts by weight of poly-vinylphenol partially protected by tert-butyl acetate, and 1 to 30 parts by weight of phenylsulfonylacetonitrile. ### Claim 29 A photosensitive composition, comprising: an alkali-soluble resin; a dissolution inhibitor which has a substituent group decomposable by an acid and generates an alkali-soluble group upon decomposition of the substituent group, or an aminoplast resin which is capable of crosslinking the alkali-soluble resin in the presence of an acid; and a compound which generates an acid upon exposure, which is selected from the group consisting of the compounds represented by formulas (1) and (3) given below: ##STR101## wherein R.sub.11 represents a monovalent organic group, or a monovalent organic group into which at least one substituent selected from the group consisting of a halogen atom, a nitro group, and a cyano group is introduced, each of R.sub.12, R.sub.13, and R.sub.14 independently represents hydrogen, a halogen atom, a nitro group, a cyano group, a monovalent organic group, or a monovalent organic group into which at least one substituent selected from the group consisting of a halogen atom, a nitro group, and a cyano group is introduced, each of R.sub.21 and R.sub.23 independently represents a monovalent organic group, or a monovalent organic group into which at least one substituent selected from the group consisting of a halogen atom, a nitro group, and a cyano group is introduced, R.sub.22 represents a sulfonyl or carbonyl group, each of R.sub.31, R.sub.32, and R.sub.35 independently represents a monovalent organic group, or a monovalent organic group into which at least one substituent selected from the group consisting of a halogen atom, a nitro group, and a cyano group is introduced, R.sub.33 represents hydrogen, a monovalent organic group, or a monovalent organic group into which at least one substituent selected from the group consisting of a halogen atom, a nitro group, and a cyano group is introduced, and R.sub.34 represents a sulfonyl group, a sulfinyl group, a sulfur atom, and a carbonyl group, and wherein the solubility of said composition in an alkali solution is changed when exposed to radiation. ### Claim 30 (depends on 29) The composition of claim 29, wherein said composition contains a polyimide precursor. ### Claim 31 (depends on 29) The composition of claim 29, wherein said composition contains an epoxy resin. ### Claim 32 (depends on 1, 11, 19) A pattern formation process, comprising the steps of: coating a substrate with a solution of the photosensitive composition according to any one of claims 1, 11 or 19 to form a resist film, wherein the composition of claim 19 may contain the aminoplast resin which has a substituent group capable of crosslinking the alkali-soluble resin in the presence of an acid instead of said compound which has a substituent group decomposable by an acid and generates an alkali-soluble group upon decomposition of the substituent group; pattern-exposing said resist film to radiation; baking the resist film after exposure to the radiation; and developing the resist film after the baking step.